Poly(thioesters), their applications and derivatives

ABSTRACT

A composition of the formulae MZAORS n R 1 F 1   m OAZ 1 M 1 , wherein O and S have their normal meaning of oxygen and sulfur, n is at least 2 and not more than 8, F 1  is of the formula —OAORS n R 1 —, m is at least 1, Z and Z 1  are the same or different and are oxy or amino, M and M 1  are the same or different and are hydrogen or an organic substituent, R and R 1  are the same or different and are organic divalent radicals, each having from 2 to 20 carbon atoms, and A is the residue of a dicarboxylic acid of from 2 to 40 carbon atoms.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of and claims priority to U.S. patentapplication Ser. No. 13/754,375 filed Jan. 30, 2013, published as U.S.Patent Application Publication US 2013/0211114 A1, which is a divisionalapplication to U.S. patent application Ser. No. 13/427,279 filed Mar.22, 2012, now U.S. Pat. No. 8,378,060, which is a divisional applicationto U.S. patent application Ser. No. 11/478,455 filed Jun. 28, 2006, nowU.S. Pat. No. 8,158,726, which is a continuation-in-part of U.S. patentapplication Ser. No. 10/826,216 filed Apr. 16, 2004, now U.S. Pat. No.7,087,708, which claims priority to U.S. Provisional Application No.60/463,123 filed Apr. 17, 2003, each of which is hereby incorporatedherein by reference in its entirety for all purposes.

BACKGROUND

Technical Field

The present invention relates generally to synthetic chemistry. Moreparticularly, the present invention relates to poly(thioesters),monomeric diesters and their derivatives. Further, the field of thisinvention is polysulfur-containing polymeric ester compositions andtheir polymers.

Background of the Invention

Despite the mature nature of the field of polymers, there remain manyopportunities to create polymers having novel properties andapplications. Polymers may be divided into addition polymers andcondensation polymers. Among the condensation polymers are polyesters,polyethers, polyurethanes, polyamines, and polyanhydrides. Thesepolymers find wide application in areas of molded products, lubricants,sealants, coatings, paints, films, fibers, elastomers and otherformulations. Their properties vary widely depending upon the functionalgroups employed, both as to nature and diversity, the backbone units,the functionalities in the backbone, the molecular weight andhomogeneity of molecular weight range of the polymeric molecules, andthe like. Because of the great diversity of properties of the polymers,there can be numerous customized applications for the polymers, wherethe properties of the polymers are customized to a particular need.

Polymers containing polythioalkyl groups have not found extensiveemployment in the polymeric field, with the exception of the Thiokol®polymers that currently are not widely used due to environmentalconcerns. Yet, the presence of sulfur in the polymers can have desirableproperties. Some polymeric products containing polysulfide linkages havebeen reported for a variety of purposes, such as polymers havingdisulfide and ether groups, disulfide and carbamate groups, anddisulfide and acetal groups in the polymer backbone. There have beenreports of other polymeric compositions, where the disulfide is in aside chain of the polymer, as in addition polymers of acrylics. Whilespecific compounds having sulfides having greater than one sulfur aredisclosed in the literature, for the most part they are not exemplifiedin the experimental work. Specifically, there have been no reports ofpolymers employing a monomeric unit of a polysulfide functionality inthe backbone and formed from a combination of a polysulfide-containingdiol and a dibasic acid.

RELEVANT LITERATURE

Ethers of di(hydroxyethyl)sulfide and -disulfide are reported in U.S.Pat. No. 2,582,605. Polymers of alkyldisulfides terminating in hydroxylgroups and further reacted with polyurethanes are reported in U.S. Pat.No. 3,386,963. Polymers of polymerized thiodiglycol reacted to provideterminal halide groups which are then further reacted with sodiumpolysulfide to form a latex dispersion are reported in U.S. Pat. No.4,124,645. Polymers of polymerized sulfide and polysulfide glycolsterminated with mercaptans are reported in U.S. Pat. No. 4,764,299. U.S.Pat. No. 6,383,324 reports the polymerization of a “randomly copolymericpolyacetal of a dithiodialkylene glycol” with polyisocyantes. Sulfursubstituted acrylic polymers are reported in U.S. Pat. Nos. 4,131,716and 6,114,485.

Hydroxyl groups that are in the β-position relative to a sulfur atom inan aliphatic chain have unusually high reactivity, and their propertiesare significantly different from other hydroxyl groups. For example,unlike compounds with hydroxyl groups in other positions, compounds withhydroxyl groups in the β-position relative to a sulfur atom in analiphatic chain readily undergo self-polycondensation as well asco-condensation with other glycols in the presence of other acids and/orat elevated temperatures, resulting in the formation of poly(thioethers)(F. Richter, et. al., U.S. Pat. No. 2,582,605).

Di(hydroxyethyl)disulfide, as well as other di(hydroxyethyl)polysulfidesare typical compounds with hydroxyl groups in the β-position relative toa sulfur atom. They are known in the art to be precursors for variouspoly(thioethers), which have been used in lubricants (U.S. Pat. No.2,582,605), in polyurethanes (U.S. Pat. No. 3,386,963), inmercaptan-terminated oligomers (U.S. Pat. No. 4,124,645), intransmission fluids (U.S. Pat. No. 4,764,299), and in acetal-functionalcompounds used in window insulation (U.S. Pat. No. 6,383,324).

The prior art describes several attempts to convertdi(hydroxyethyl)polysulfides into various compounds that contain esterfunctionality adjacent to the —(CH₂)_(n)—S— segment. For example, U.S.Pat. No. 6,114,485 discloses compounds that include an —O—C(O)—(CH₂)₂—S—segment in monomeric products, but the chemical structure of thesecompounds is achieved through a chain of several complex chemicalreactions that take multiple steps and over 20 hours of combinedreaction time. In addition, the technology described in this patentcannot be used to produce polymeric products with multiplepoly(thioester) segments.

U.S. Pat. No. 2,221,418 by Weihe et al. (referred to hereafter as Weihe)and U.S. Pat. No. 5,407,972 by Smith et al. (referred to hereafter asSmith) describe products that are produced after (polythio)glycols aremixed with dicarbonic acids and/or their anhydrides. However, thesepatents do not describe the formation of poly(thioesters) from theseproducts. For example, Weihe describes the formation of an “insolublebalsam”, and Smith describes “polysulfide polymers” produced as theresult of the interaction between di(hydroxyethyl)polysulfides anddibasic carbonic acids or their anhydrides.

Nowhere in Weihe or Smith is described the chemical structure of theresulting products. However, based on the above-described unusualreactivity of hydroxyl groups in the β-position relative to a sulfuratom, and the strong tendency of such hydroxyl groups to homo-condenseaccording to reaction (1), it is highly likely that the products formedby Weihe and Smith under the conditions described in these patents arepoly(thioethers), rather than poly(thioesters).mHO—(CH₂)₂—S_(x)—(CH₂)₂—OH→H(—O—(CH₂)₂—S_(x)—(CH₂)₂)_(m)—OH+(m-1)H₂O  (1)

In the case where the products were formed with the participation ofdibasic carbonic acids, they would likely form a solution of dibasiccarbonic acids in solid or semi-solid poly(thioether) resins. In thecase where the products were formed with the participation of anhydridesof dibasic carbonic acids, the solid or semi-solid poly(thioether)resins would have a chance to react with anhydrides. This would allowthe formation of a randomly-formed compound with no more than tworadicals per molecule and a single ester structure for each radical. Aregular poly(thioester) polymer would not be formed.

The absence in the prior art of the description of regularpoly(thioesters) produced from compounds with hydroxyl groups in theβ-position relative to a sulfur atom is further illustrated by Wilson inU.S. Pat. No. 5,342,724 (referred to hereafter as Wilson). Wilsondescribes the formation of multiple poly(thioesters) fromsulfur-containing diols and dibasic carbonic acids. However, allsulfur-containing diols with hydroxyl groups in the β-position relativeto the sulfur atoms were left out from the list of diols mentioned byWilson, as the state-of-the art technology available at the time did notallow production of poly(thioesters) from such compounds.

Accordingly, there is a need in the art to develop methods of formingpoly(thioesters) from sulfur-containing diols with hydroxyl groups inthe β-position relative to the sulfur atoms.

SUMMARY OF THE INVENTION

Compositions are provided comprising the condensation product of twocompounds: a dibasic acid, or its anhydride and a di(hydroxy substitutedorganic group)polysulfide, where the compositions have one or aplurality of units consisting of the combination of the two compounds.The compositions are formed by combining the compounds under selectedacidic conditions and at a mole ratio to provide the desired product.The compositions resulting from the reaction will usually be a mixturein the absence of a large excess of one of the reactants, unless specialconditions to prevent oligomerization are employed. Depending on theratios of the two reactants the majority of molecules in the compositionmay have one hydroxyl and one carboxyl as terminating groups, or twohydroxyls or two carboxyls. All of these compounds may react with a widevariety of polyfunctional compounds to provide products havingproperties applicable for specific end purposes.

In an embodiment, the present invention provides poly(thioesters),produced from di(hydroxyethyl)polysulfides and various dibasic carbonicacids or their anhydrides, and their derivatives. The newpoly(thioesters) combine properties of polyesters and polysulfides. Thepoly(thioesters) can be used as components in many compositions,including but not limited to adhesives, sealants, caulks, coatings,plastics, paints and elastomers.

In one embodiment, the poly(thioesters) have the formula:R²—[—O-A-O—α-]_(n)—O-A-O—R²

-   -   wherein    -   each R² is H or R¹-f,        -   wherein R¹ is any bi-valenced organic radical, and            -   f is H or any reactive functional group;    -   each R² is the same or different;    -   A is either X or Y,        -   wherein X is            —(—(CH₂)₂—S_(x)—(CH₂)₂O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—,            -   Y is —C(O)—R¹—C(O)—,            -   m is at least zero, and            -   x is between two and six;    -   B is either Y or X;    -   O, H, C, and S have their normal meaning of oxygen, hydrogen,        carbon, and sulfur;    -   if A is X, then B is Y;    -   if A is Y, then B is X; and        n is at least one, except for the case when A is Y, B is X, R¹        is a dibasic carbonic acid that is a cyclic anhydride or forms a        cyclic anhydride, and R² is H, in which case n is at least two.

In another embodiment, the poly(thioesters) have the formula:f ¹-R¹—NH-A-O—B—[—O-A-O—B—]_(n)—O-A-HN—R¹-f ¹

-   -   wherein    -   A is —C(O)—R¹—C(O)—;    -   B is —((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;    -   R¹ is any bi-valenced organic radical;    -   m is at least zero;    -   n is at least one;    -   x is between two and six;    -   f¹ is a hydroxyl, a primary amine group, a secondary amine group        or a tertiary amine group; and    -   O, H, C, S, and N have their normal meaning of oxygen, hydrogen,        carbon, sulfur and nitrogen.

In yet another embodiment, the poly(thioesters) have the formula:R³—C(O)—[—O-A-O—B—]_(n)—O-A-O—C(O)—R³

-   -   wherein    -   A is —((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;    -   B is —C(O)—R¹—C(O)—;    -   R¹ is any bi-valenced organic radical;    -   m is at least zero;    -   n is at least one;    -   x is between two and six;    -   R³ is R¹-f², HN—R¹-f³, or HN—R⁴—NCO,        -   wherein f² is a chemical structure or functional group;            -   f³ is a chemical structure of functional group; and            -   R⁴ is a radical that is located between two isocyanate                groups of a di- or polyisocyanate; and    -   O, H, C, S, and N have their normal meaning of oxygen, hydrogen,        carbon, sulfur and nitrogen.

In an additional embodiment, the poly(thioesters) have the formula:H—R⁵—[—O-A-O—B—]_(n)—O-A-R⁶—OH

-   -   wherein    -   A is —((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;    -   B is —C(O)—R¹—C(O)—;    -   R¹ is any bi-valenced organic radical;    -   m is at least zero;    -   n is at least one;    -   x is between two and six;    -   R⁵ is H [O—CH₂—CHR³]_(q-k) or [O—CHR³]_(q-k);    -   R⁶ is [O—CHR³—CH₂]_(q) or [O—CHR³]_(k);    -   if R⁵ is H[O—CH₂—CHR³]_(q-k), then R⁶ is [O—CHR³—CH₂]_(q);    -   if R⁵ is [O—CHR³]_(q-k), then R⁶ is [O—CHR³]_(k);    -   R³ is either H or methyl;    -   q is at least one;    -   q is greater than or equal to k;    -   and O, H, C, S, and N have their normal meaning of oxygen,        hydrogen, carbon, sulfur and nitrogen.

In an embodiment, the present invention further provides novel monomericdiesters. The new monomeric diesters are produced fromdi(hydroxyethyl)polysulfides and various monobasic carbonic acids ortheir anhydrides. The monomeric diesters have use as components in manycompositions, including but not limited to solvents and plasticizers.

Monomeric diesters according to the present invention have the formula:R⁷—C(O)—O—X—O—C(O)—R⁷

-   -   wherein X=—(—(CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;        -   R⁷ is either H, or any monovalent organic radical;        -   each R⁷ is either the same or different;    -   m is at least zero;        -   x is at least one; and    -   O, H, C, and S have their normal meaning of oxygen, hydrogen,        carbon, and sulfur.

BRIEF DESCRIPTION OF THE FIGURES

The present invention together with its objectives and advantages willbe understood by reading the following description in conjunction withthe drawings, in which:

FIG. 1 compares IR spectra of products made according to Weihe andpoly(thioesters) according to the present invention.

FIG. 2 compares IR spectra of products made according to Wilson andpoly(thioesters) according to the present invention.

DESCRIPTION OF THE SPECIFIC EMBODIMENTS

In accordance with the subject invention, compositions are producedusing a combination of a polysulfide-containing diol and a dibasiccarboxylic acid. The products have polysulfide and ester linkages intheir backbone. Each of the molecules will have at least one unit thatincludes one oxy group, one carbonyl group, one organic ester group, apolysulfide group, and will have at least 5, usually at least 6 carbonatoms, more usually at least 8 carbon atoms and not more than about 80carbon atoms, usually not more than about 60 carbon atoms, more usuallynot more than about 46 carbon atoms. The sulfur atoms will be at leastabout 2 carbon atoms from an oxygen atom.

Products comprising the units can be prepared by combining the tworeactants, desirably in the presence of acid, at an elevated temperatureand removing water as formed. Depending on the conditions, products maybe prepared using about 1:1 mole ratios of reactants and havingpredominantly hydroxyl and carboxyl groups at the termini, where theproducts are homopolymers or oligomers generally having more than abouttwo units and having molecular weights of 5000 dal or more, or usingmole ratios between greater than 1:1 and 1:2 and having predominantlyterminal hydroxyl groups or carboxyl groups. As indicated above, byusing special conditions or large excesses of one of the reactants amore homogeneous composition may be obtained where the ratio of thereactants is 1:2 and has a defined composition.

In referring to a homopolymer or homopolymers, it is intended that thecombination of one di(hydroxysubstituted organic group) and one dibasicacid form a repetitive unit and the molecules will have both hydroxyland carboxyl termini. An “extended monomeric” unit will have a ratiobetween greater than 1:1 and up to 1:2 of the two reactants, so thatthere will be a majority of terminal groups of the same functionality,where extended monomeric unit molecules can be employed as monomers.Particularly with co-polymers, the extended monomer will be preferred tocorrespond to monomers having a plurality of the same functionality.

Each product includes a monomer unit with the following formula:—ORS₁R¹OA- or —OAOR¹S_(n)R—wherein:

O and S have their normal meaning of oxygen and sulfur;

n is at least 2 and not more than about 8, usually not more than about4, generally ranging from 2-4, more usually from 2-3;

R and R¹ are the same or different and are organic divalent radicals,usually aliphatic and more usually hydrocarbon, saturated orunsaturated, straight or branched chain, generally R and R¹ having from2 to 20, more usually 2 to 12 carbon atoms, wherein the total number ofcarbon atoms for R and R¹ will be in the range of about 4 to 40, usually4 to 24 carbon atoms; and

A is the residue of an organic dibasic carboxylic acid (lacking the twohydroxyl oxygens set forth in the formula) having from at least onecarbon atom and not more than about 60 carbon atoms, generally fromabout 2 to 60, more usually about 2 to 40, frequently about 2 to 12, andconveniently about 2 to 6 carbon atoms, for acids formed by other thandimerization of two monobasic carboxylic acids and from about 24 to 40carbon atoms for fatty acid dimers.

Where the composition is formed from the reactants in a mole ratio ofits reactants of between about 1:1 and up to and including 2:1 or evengreater, and has molecular weight below about 5000 dal, it is referredto as “extended monomer;” the extended monomer will have one of thefollowing formulae:MF_(m)ORS_(n)R¹OM¹; or  (a)MZAORS_(n)R¹F¹ _(m)OAZ¹M¹,  (b)wherein

O and S have their normal meaning of oxygen and sulfur;

n is at least 2 and not more than about 8, usually in the range of about2 to 4, more usually in the range of 2 to 3;

F is of the formula —ORS_(n)R¹OA-;

F¹ is of the formula —OAORS_(n)R¹—;

m is at least 1;

Z and Z¹ are oxy or amino;

M and M¹ are the same or different and are hydrogen when only a dibasicacid and a di(hydroxysubstituted organic group)polysulfide are reacted,or an organic substituent bonded to oxygen to form an ether or ester asappropriate or nitrogen to form a substituted amino or amide, when witha single group it is referred to as an “augmented extended monomer;” and

the remaining symbols are as defined previously.

The extended monomers and augmented monomers can be used to form homo-or copolymers (of the extended monomers, only the hydroxyl terminalextended monomers can be used to form homopolymers).

R and R¹ may be ethylene, propylene, isopropylene, butylene, hexylene,hexenylene, butynylene, etc.

Preferred polysulfide diol compounds are aliphatic, where R and R¹ aredialkylene of from 2-12, usually 2 to 6 carbon atoms, particularlypolymethylene, or methyl or ethyl substituted polymethylene. Preferably,the hydroxyl group is from 2 to 3 carbon atoms from the polysulfidegroup.

Examples of A include carbonyl dioyl, (carbonic acid; particularly whenin a 1:2 mole ratio to the diol) oxaldioyl, malondioyl, succindioyl,pimeldioyl, adipdioyl, sebacdioyl, maledioyl, phthaldiolyl,terephthaldioyl, dimers of fatty acids (particularly fatty acids of from16 to 18 carbon atoms), oxy(bis-acetyl), N-methyl amino(bis-propionyl),1,4-cyclohexane diacetyl, etc. Preferred A groups are aliphatic, may besaturated or unsaturated, straight chain or branched and may have 0 to 2heteroatoms, such as oxygen, nitrogen and sulfur.

Z and Z¹ are the same or different and will be for the most part oxy or—NH—, but may be a substituted amino having an alkyl group of from 1 to6, usually 1 to 2 carbon atoms.

When M and M¹ are other than hydrogen, that is, define the “augmentedextended monomer,” then

M is defined as WR²—; and

M¹ is defined as W¹R³—,

wherein:

R² and R³ are the same or different and organic divalent radicals,normally terminating in carbon atoms, of 1 to 20 carbon atoms, usually 2to 12 carbon atoms, which may be aliphatic, alicyclic, aromatic,heterocyclic (usually having from 1-3, more usually 1-2, annularheteroatoms, that are oxygen, nitrogen and sulfur) or combinationsthereof, usually aliphatic, substituted or unsubstituted, straight orbranched chain, aliphatically saturated or unsaturated, usually havingno more than three, more usually no more than two sites of aliphaticunsaturation, e.g. double or triple bond, conjugated or unconjugated,where substituents not participating in the reaction to form theaugmented monomer will be inert to the reactions of preparation of theaugmented monomers and may be inert to the polymerization reactions,being organic or inorganic substitutions, containing heteroatoms such asoxygen, nitrogen, sulfur, phosphorous, silicon, boron, etc., comprisingsuch groups as oxy (ether), thio (usually ether), cyano, amino andsubstituted amino, I°, II°, III° and IV′, halo, azo, etc., oxo-carbonyl(keto, aldehyde), non-oxo-carbonyl (carboxylic acid, ester and amide)phosphoryl, phosphonyl, silicyl, boronyl, etc., there usually being notmore than about 4 heterosubstituents, more usually not more than about 2heterosubstituents, generally having from 2 to 12, more usually 2 to 6carbon atoms, and from 0 to 8, more usually 0 to 6, generally 0 to 4heteroatoms; generally being aliphatic of from 2 to 6 carbon atoms,particularly polymethylene or methyl or ethyl substituted polymethylene;and

W and W¹ are the same or different, usually the same, and are amino,including primary and secondary amino of from about 1 to 6, usuallyabout 1 to 4 carbon atoms, hydroxyl, carboxyl, isothiocyanate,isocyanate, oxo-carbonyl, non-oxy-carbonyl, siloxane, silane,cyclocarbonate, active olefin, e.g. acrylyl, methacrylyl, allyl, vinyl,e.g. vinyl ether, active halo, and the like.

Compounds that can be used to further augment the size of the extendedmonomers include diamines, such as propylene diamine, N-methylbutylenediamine, N-aminoethylpiperazine, 1,1-dimethyl-1,4-diaminobutane,trimethylhexamethylenediamine, 2-methylpentamethylenediamine, aziridine,oxirane, glycidyl alcohol, diols, such as diethylene glycol,tripropylene glycol, catechol, hydroquinone, various dihydroxyalkylpolysulfides, glycolic, acrylic and methacrylic acids, hydroxyethylacrylate and methacrylate, N-hydroxypropyl acrylamide, di(hydroxybutyl)diethyl siloxane, allyl alcohol, glycerol carbonate, chloroacetic acid,acrylic acid, dihydroxyacetone, 4,4-di(hydroxymethyl)butyric acid, etc.

The extended monomers and the polymers of the basic unit of thepolysulfide diol and dibasic acid may be prepared by combining the tworeactants in the appropriate mole ratio, depending upon which monomer isdesired and whether terminal hydroxyl or terminal carboxyl groups aredesired. The polysulfide diol and diacid or anhydride are combined inthe appropriate ratio, conveniently in the absence of a solvent and inthe presence of an acid catalyst, and heated to an elevated temperatureabove about 90° C., generally in the range of about 100 to 180° C.,while removing the water from the reaction mixture. Water can be removedconveniently by employing a mild vacuum, from about 1-20 mm Hg. Anyconvenient acid catalyst may be employed, although it is found that forsome combinations, one catalyst is preferred over another. For the mostpart, sulphonic acid catalysts find use, particularly methane sulfonicacid, although p-toluene sulphonic acid may also be used. Othercatalysts include zeolites, Lewis acids, acidic diatomaceous earths,etc. The amount of catalyst will generally be in the range of about 0.01to 2 wt % of the reactants. In some instances, mixtures of the diol maybe employed, where the polysulfide may be a mixture of polysulfideshaving differing numbers of sulfurs. For example, the commerciallyavailable DiHEDS (Chevron Phillips Chemical Company LP, regular grade)comprises 95-97% di(hydroxyethyl)disulfide and 3-5% of higherpolysulfides, mainly the trisulfide.

The high molecular weight poly(thioesters) have the formula:Xf _(m)OX¹wherein:

f is the group —ORS_(n)R¹OA-;

X is H or HOA-;

X¹ is H or —RS_(n)R¹OH;

m is in the range of about 2 to 100, usually in the range of about 2 to60, more usually in the range of about 4 to 50; and

the remaining symbols are as defined previously.

These polymers can be produced when the molar ratio between dibasic acidand a di(hydroxysubstituted organic group)polysulfide is close to 1:1,or equals 1:1.

The subject monomers may be reacted with difunctional compounds havingthe same or different functionalities, where the difunctional compoundswill generally be of at least about 2 carbon atoms, usually when amonomer of from about 2 to 12, more usually 2 to 6 carbon atoms andusually having only two reactive functionalities, although up to 4reactive functionalities may be present if one wishes to havecross-linking, or 1000 or more carbon atoms, usually not more than about500 carbon atoms when one wishes prepolymers. Common reagents includeglycolic acid, where a terminal hydroxyl may be exchanged for a carboxylfunctionality or a terminal carboxyl functionality may be extendedretaining the carboxyl functionality. Therefore, by appropriate choice,one may vary the terminal functionalities depending upon the comonomerthat one wishes to use for the copolymerization. Functionalities forreacting with the monomer may include active halogen, hydroxyl, andcarboxy, while the terminal functionality may include active halogen,non-oxo- and oxo-carbonyl, hydroxyl, amino, e.g. primary and secondary,silyl, siloxanyl, etc. For cross-linking, combinations of hydroxyl,carboxyl, amino, etc. functionalities may be employed, having at leastabout 3 and not more than about 5 reactive functionalities.

The polymers of the extended monomers and augmented monomers may begenerally depicted with the following formula:T(ED)_(r)T¹wherein:

T and T¹ are the same or different and are the terminal groups of thepolymer derived from one of the comonomers;

one of E and D is a subject extended and/or augmented monomeric unit,and the other is the comonomer; and

r will be at least 2, generally on the average at least about 5 andusually not more than about 1000, more usually not more than about 500,generally not more than about 100.

The polymers that are prepared will have at least one extended and/orextended augmented monomeric unit, generally at least two of such units,and may have 500 or more of such units, depending upon the nature of thepolymer. One group of polymers of particular interest are polymers thathave from about 2 to 100, more usually about 5 to 50 total monomericunits, coming from both the subject extended monomers and thecomonomers. The same or different subject extended monomers may be usedand the polymers may include block copolymers, alternating copolymers,cross-linked copolymers, etc. The comonomer may be a small di- or higherfunctionality molecule of less than about 500 dal, may be an oligomer of2 or more units, usually not more than about 100 units, or any otherorganization of monomers to provide the second member of the copolymer.As indicated above, one may have a condensation polymer where thesubject monomers are in the backbone of the polymer or may be joined toa monomer that can undergo addition polymerization, where the subjectmonomer would be a side chain or a cross-linker for the polymer.

A variety of second monomers can be employed to provide the polymericproducts of this invention. One important group of compounds ispolyisocyanates to form polyurethanes. Illustrative polyisocyanatesinclude 2,4- and 2,6-toluene diisocyanate, isophorone diisocyanate,trimethylhexamethyleneisocyanate, 3,3′-dimethoxy-4,4′-biphenylenediisocyanate, naphthalene-1,5-diisocyanate, hexamethylene diisocyanate,1,4-phenylene diisocyanate, etc. Illustrative patents concerningdiisocyanates are U.S. Pat. Nos. 4,032,468; 5,043,398 and 5,098,788 andthe references cited therein, are specifically incorporated herein byreference and are only illustrative of the large patent literatureconcerning the use of polyisocyanates with a wide variety of comonomersfor a diverse group of utilities.

The polyurethanes can be prepared from hydroxy-terminated extendedmonomers by their reaction with polyisocyanates, and fromisocyanate-augmented expended monomers by the reactions withconventional polyol and polyamine chain extenders and crosslinkers inaccordance with conventional ways as described in the references citedabove and other references present in the literature. Generally, thereaction takes place at temperatures in the range of about 20 to 150° C.in the presence of typical catalysts of an isocyanate reaction, whichare known to persons skilled in the art. The ratio of NCO to OH shouldbe chosen depending on the targeted properties of the produced material:if the goal is to produce a hard polyurethane plastic, or polyurethaneelastomer, the NCO/OH ratio should be close to 1:1. If the goal is toproduce a curable reactive resin or prepolymer, the ratio should behigher. The time of the reaction will vary depending upon the nature ofthe reactants, generally not exceeding several hours.

Also important are products generated when the carboxyl andhydroxyl-terminated extended monomers and augmented monomers arepolymerized through the reactions of polyetherification,polyesterification and polyamidation, where the hydroxyl or carboxylgroups of the monomer may react with amine or hydroxyl groups of apolyfunctional co-reactant, forming a polymer with amide, ether andester links. In this way, polymers can be prepared having a variety ofphysical and chemical properties. The comonomers in these reactions arepolyamines, polyethers or combinations thereof, where the comonomers maybe di- or higher order, being aliphatic, alicyclic, aromatic orcombinations thereof, substituted or unsubstituted, the substituentsnormally being inert in the polymerization, such as ethers, esters,amides, cyano, stable halo, e.g. bonded to an annular aromatic carbon,etc., or may be heterocyclopropanes, i.e. aziridine, oxirane andsubstituted derivatives thereof, where the subsistent will usually bealkyl. Thus, comonomers may be exemplified by ethylene glycol, propyleneglycol, polyethylene glycol, di(hydroxyethyl)amine, di(aminoethyl)ether,N-methyl di(aminoethyl)ether, di(hydroxyethyl)sulfide or disulfide,hydroquinone, catechol, 1,4-diaminocyclohexane, 1,4-phenylenediamine,etc. The comonomers will have from about 2 to 20, more usually fromabout 2 to 12 carbon atoms and from 2 to 7, usually 2 to 5 heteroatoms,which will for the most part be N, S and O.

Instead of the condensation polymers described above, the subjectmonomers may be modified to be used in addition polymers. By modifying ahydroxyl or carboxyl group to add an addition polymerizable olefinicgroup, one can provide products that can serve as addition polymerizablemonomers where only one olefinic group is added or as cross-linkingagents, where two olefinic groups are added. In the latter case, bycopolymerizing with a different addition polymerizable monomer, one canprovide a polymer that is reversibly cross-linked. By reducing adisulfide linkage, the cross-linking will be cleaved, while withoxidation the disulfide will be restored and the cross-linkreestablished.

Any convenient addition polymerizable compound can be employed that willreact with a hydroxyl group or carboxyl group of the subject extendedmonomers and with the same functionalities as well as amino groups ofthe subject augmented monomers. Thus any active ethylene group that hasan available hydroxyl, carboxyl or amino group for reaction can beemployed. For example, the acrylic acids, hydroxysubstituted activeethylene groups, e.g. hydroxyethoxyethylene, aminoethoxyethylene,aminoethyl acrylate, hydroxyethyl acrylamide, etc. Common additionpolymerizable monomers useful as comonomers include the acrylic acids,such as acrylic acid, methacrylic acid, α-chloroacrylic acid, ethylacrylate, acrylamide, etc., vinyl compounds, such as hydroxyethyl vinylether, carboxyethyl vinyl ether, vinyl glycolate, allyl alcohol, etc.,and polyenes, such as 2-hydroxymethyl butadiene, carboxymethylbutadiene, p-carboxystyrene, etc.

The polymers may be formulated in conventional ways. Common additivesinclude plasticizers, extenders, UV absorbers, stabilizers, releaseagents, etc. These additives are used based on the nature of the polymerin conventional amounts or reduced amounts based on the propertiesprovided by the subject monomers.

These compounds will be prepared in accordance with conventional ways,where esters can be prepared with carbodiimides, mixed anhydrides, oracid, as appropriate, with removal of water, and the like, under mildconditions, by combining the reactants in the appropriate mole ratio.The addition polymers may be polymerized under conventional conditionsthat are compatible with the presence of a polysulfide. Acid, metal ionor actinic radiation, optionally in conjunction with a photoinitiator,catalysis can find use. See, for example, U.S. Pat. No. 4,131,716.

While the above described polymers are the most common polymers, thesubject monomers can also find use with such polymers as polyacetals,polyphosphate esters, alkyd polymers, polydienes, poly fatty acids, andthe like.

The subject monomers can impart a large number of advantageousproperties to the polymers employing the monomers. The subject monomerscan enhance flexibility, low temperature properties, hydrophobicity,non-polar organic solvent resistance, affinity to metal surfaces, evenrusty metal surfaces, weatherability, including ozone resistance, gasimpermeability, resistance to UV radiation, mechanical properties andabrasion resistance, particularly in conjunction with polyisocyanatecomonomers.

Due to the compatibility of the subject monomers, they can find use inpolymers used as adhesives, sealants, coatings, elastomers, plasticformulations, molded products, fibers, hot melt adhesives, as additivesand modifiers and independently as precursors to other reactivecompounds. A variety of physical objects can be made having varyingcharacteristics and properties from the polymers, using the subjectpolymers by themselves or in combination with other compatible polymers.

Embodiments of Poly(Thioesters)

In an embodiment, the present invention provides poly(thioesters) of theformula:R²—[—O-A-O—B—]_(n)—O-A-O—R²

wherein

R² is H;

A is either X or Y,

-   -   wherein X is —(—(CH₂)₂—S_(x)—(CH₂)₂O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—,        -   Y is —C(O)—R¹—C(O)—,        -   R¹ is any bivalenced radical,        -   m is at least zero, and        -   x is between two and six;

B is either Y or X;

O, H, C, and S have their normal meaning of oxygen, hydrogen, carbon,and sulfur;

if A is X, then B is Y;

if A is Y, then B is X; and

n is at least one, except for the case when A is Y, B is X, and R¹ is adibasic carbonic acid that is a cyclic anhydride or forms a cyclicanhydride, in which case n is at least two.

Poly(thioesters) according to the present invention are made fromreacting two main components. The first component includesdi(hydroxyethyl)polysulfides, homopolymers of di(hydroxyethylpolysulfides), or a mixture of di(hydroxyethyl)polysulfides andhomopolymers of di(hydroxyethyl)polysulfides. The second componentincludes dibasic carbonic acids and their anhydrides, or mixtures ofdibasic carbonic acids and their anhydrides. The two components arereacted in the presence of a protonic acidic catalyst at a temperatureof between about 80° C. and about 130° C.

Any type of protonic acidic catalyst may be used according to thepresent invention. Preferably, the acidic catalyst is a nonoxidizingprotonic acidic catalyst. More preferably, the acidic catalyst ismethanesulphonic acid. When methanesulphonic acid is used as thecatalyst, the two components may be reacted at a temperature of betweenabout 80° C. and about 180° C.

Any di(hydroxyethyl)polysulfides (or homopolymers thereof) may be usedaccording to the present invention. Preferably, thedi(hydroxyethyl)polysulfide is a di(hydroxyethyl)disulfide, adi(hydroxyethyl)trisulfide, or a di(hydroxyethyl)tetrasulfide.

Any dibasic carbonic acid or its anhydride may be used according to thepresent invention. Preferred dibasic carbonic acids are C₂ to C₄₀saturated and unsaturated acids, substituted and unsubstitutedcarboxylic diacids and their anhydrides. Examples include, but are notlimited to, fatty acid dimers, malonic, succinic, glutaric, adipic,pimelic, suberic, azelaic, sebacic, maleic, fumaric, phthalic,isophthalic, terephthalic, hemimellitic, trimellitic, trimesic,nonane-dicarbonic, decane-di-carbonic, brassylic, dithiodiacetic,dithiodipropionic, and dithiodibutyric acids and their anhydrides. Inaddition, mixtures of dibasic carbonic acids or their anhydrides may beused to make poly(thioesters) according to the present invention. Thoughthe chemical reactions shown below illustrate the interaction betweendi(hydroxyethyl)polysulfides and dibasic carbonic acids, any personskilled in the art can understand that similar reactions can occur whenthe anhydrides of dibasic carbonic acids are taken in the place of theacids themselves.

The structure, molecular weight and other properties of poly(thioesters)can be varied by a person skilled in the art within a wide range ofparameters to achieve targeted properties of the final polymer. Themechanisms that allow such a variation in properties include selecting adibasic carbonic acid with a particular structure, and properly choosingits molar ratio with di(hydroxyethyl)polysulfide or its homopolymer.These mechanisms make it possible to obtain both carboxyl- andhydroxyl-terminated poly(thioesters) with different pre-regulatedlengths of polymeric chain, as well as high molecular weightpoly(thioester) polymers. In particular, varying the structure of thecarboxyl-carrying participants in the reaction, and the molar ratio ofthe reactants, allows producing poly(thioesters) with the

-   -   desired type of termination (carboxyl- and hydroxyl-terminated        compounds),    -   desired structure of repetitive polymeric segment, and    -   desired number of such segments per molecule, i.e. molecular        weight of the product.

Varying the molar ratio of components between 1:1 and 2:1 allows theproduction of poly(thioesters) containing the desired number ofpolysulfide segments and ester groups. If the molar ratio of reactantsis close to 2:1, low molecular weight or oligomeric compounds areproduced. If the molar ratio of reactants is close to 1:1, highmolecular weight thermoplastic poly(thioesters) are produced.

Carboxyl-terminated poly(thioesters) are produced fromdi(hydroxyethyl)polysulfides and dibasic carbonic acids according toreaction (2), when the molar concentration of the carboxyl group in thereaction mixture is higher than the molar concentration of the hydroxylgroup.(n+1)HO-A-OH+nHO—B—OH→H[—O-A-O—B—]_(n)—O-A-OH+(n+1)H₂O  (2)where A=—C(O)—R¹—C(O)—

B=—((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—

m≧0

1≦n≦25.

Hydroxyl-terminated poly(thioesters) are produced according to thereaction (2),

where A=—((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—, and

B=—C(O)—R¹—C(O)—.

High molecular weight poly(thioesters) are produced when the molarconcentration of the hydroxyl group in the reaction mixtureapproximately equals the molar concentration of the carboxyl group, i.e.when in the reaction (2) n>25. In the case of high molecular weightpoly(thioesters), if one component is taken in slight excess, itstermination will be prevailing. High-molecular weight poly(thioesters)are thermoplastic materials that can be formed by extrusion, injectionor compression molding or other similar techniques.

Poly(thioesters) according to the present invention can be used as thebasis of many different compositions. Low molecular weight, oroligomeric compounds can be used as components in various adhesive,sealant, caulk, coating, paint, elastomer or other compositions. Thecarboxyl-terminated poly(thioester) oligomers can be chain extended andcrosslinked, for example, by polyaziridines, epoxies and inorganicsalts, oxides and hydroxides. The action of di- and/or polyisocyanateswill convert oligomeric hydroxy-terminated poly(thioesters) into solidpolyurethanes with a poly(thioester) backbones.

High molecular weight thermoplastic poly(thioesters) can be used for theproduction of flexible plastics, or used as an additive, which impartstargeted properties on such materials as polyethylene terephthalate, andcured unsaturated polyesters, vinyl esters, or other similar plastics.

Products Derived from Carboxyl-Terminated Poly(Thioesters)

Carboxyl-terminated poly(thioesters) can further react withhydroxyl-containing substances using an esterification mechanism to formcompounds of the formula:R²—[—O-A-O—B—]_(n)—O-A-O—R²

wherein

each R² is R¹-f,

-   -   wherein R¹ is any bi-valenced organic radical, and        -   f is H or any reactive functional group;

each R² is the same or different;

A is —C(O)—R¹—C(O)—;

B is —(—(CH₂)₂—S_(x)—(CH₂)₂O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;

-   -   wherein    -   m is at least zero;    -   x is between two and six; and

O, H, C, and S have their normal meaning of oxygen, hydrogen, carbon,and sulfur.

The esterification mechanism takes place in typical conditions for suchreactions, familiar to any person skilled in the art. Reaction (3)describes such reactionsf-R¹—OH+H[—O-A-O—B—]_(n)—O-A-OH+HO—R¹-f→f-R¹—[—O-A-O—B—]_(n)—O-A-O—R¹-f+2H₂O  (3)

-   where f is a chemical structure or functional group that introduces    special properties and characteristics, allowing further utilization    of the newly produced compound. The structure of f includes, but is    not limited to hydroxyl, acrylic, methacrylic, allyl, vinyl, maleic,    activated halogen, nitrile, cyclocarbonate, mercaptan and tertiary    amine groups.

Examples of carriers of various f functionalities include:

-   -   For hydroxyl functionality—any diol, polyol, or organic oxide;    -   For acrylic functionality—hydroxy acrylate;    -   For methacrylic functionality—hydroxy methacrylate;    -   For allyl and vinyl functionalities—any compound containing both        a hydroxyl group and an allyl or vinyl group, such as monovinyl        ether of diethyleneglycol;    -   For cyclocarbonate functionality—glycerol carbonate;    -   For amine functionality—N,N′-dialkylethanolamine;    -   For activated halogen functionality—a monoester of any glycol        and chloroacetic acid;    -   For maleic double bond functionality—maleic anhydride;    -   For nitrile functionality—ethylenecyanohydrin; and    -   For mercaptan functionality—mercaptoethanol.

One important example of reaction (3) is when f is another hydroxylgroup. Carboxyl-terminated poly(thioesters) can react with an individualpolyol, or mixture of polyols, forming, depending on thepoly(thioester)/polyols molar ratio, a blocked polymer, which includespoly(thioester) and polyether blocks. The molecular weight of the finalproduct, and the proportion of the polyester/polyether segments in itcan be pre-determined by the molar ratio of the reactive component. Forexample, if one takes 2 moles of component A and one mole of componentB, the resulting product will mostly contain molecules with molecularweight equaled to twice the molecular weight of A plus one molecularweight of B. This is the lowest molecular weight product obtained bypolycondensation (in this case it is not “polycondensation”, but plaincondensation). In contrast, if one takes 1 mole of A and 1 mole of B,one would theoretically get one polymeric molecule with molecular weightapproaching infinity. Any ratio between 1:1 and 2:1 will result in aproduct with a definite molecular weight, so that a person skilled inart can, by choosing the ratio of components, choose the molecularweight of the final product. It must be noted that if one of the polyolsthat participates in this process has functionality higher than 2, theresulting products have a degree of branching, which is pre-determinedby the molar amount of the high functionality polyol.

The products of reaction (3) with compounds other than polyols can alsobe used in various reactive formulations cured by the radical mechanismin the cases of acrylic, methacrylic, allyl and vinyl-terminatedsubstances, by the action of air moisture in the cases ofalkoxysilane-terminated substances, by diamines in the case ofcyclocarbonate-terminated materials, and by the anionic mechanism in thecase of tertiary amine-terminated materials.

Carboxyl-terminated polythioesters can further react with any compoundwith amine group(s) through an amidation mechanism to form compounds ofthe formula:f ¹-R¹—NH-A-O—B—[—O-A-O—B—]_(n)—O-A-HN—R¹-f ¹

-   -   wherein    -   A is —C(O)—R¹—C(O)—;    -   B is —((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;    -   R¹ is any bi-valenced organic radical;    -   m is at least zero;    -   n is at least one;    -   x is between two and six;    -   f¹ is a hydroxyl, a primary amine group, a secondary amine group        or a tertiary amine group; and    -   O, H, C, S, and N have their normal meaning of oxygen, hydrogen,        carbon, sulfur and nitrogen.

The amidation reactions take place in typical conditions for suchreactions, familiar to any person skilled in the art. Reaction (4)describes such reactions.f ¹-R¹—NH₂+H[—O-A-O—B—]_(n)—O-A-OH+H₂N—R¹-f ¹ →f¹-R¹—NH-A-O—B—[—O-A-O—B—]_(n-1)—O-A-HN—R¹-f ¹+2H₂O  (4)where f¹ is a hydroxyl, or a primary, secondary or tertiary amine group.

An important example of reaction (4) is when f¹ is a primary orsecondary amine group. Carboxyl-terminated poly(thioesters) can reactwith diamines, forming, depending on the poly(thioester)/diamine molarratio, either amidoamine, or polyamide with poly(thioester) segments. Ifan amidoamine is desired, in order to generate a product with the leastamount of undesirable byproducts, it is beneficial to react thecarboxyl-terminated poly(thioester) with a diamine that has unequalreactivity of amine groups, i.e. either has one primary and onesecondary amine group, such as in N-aminoethyl piperazine, or onesterically hindered amine group, such as trimethylhexamethylenediamine,2-methylpentamethylenediamine, 1,3-pentanediamine and isophoronediamine. On the other hand, if the goal of the technological process isto produce polyamide with poly(thioester) segments, it is better to usein reaction (4) a diamine with two primary amine groups with equalreactivity.

Amidoamines produced as the result of reaction (4) can be used as is, orin a mixture with other products, for example as curing agents for epoxycoatings and adhesives formulations.

Products Derived from Hydroxyl-Terminated Poly(Thioesters)

Hydroxyl-terminated poly(thioesters) can further react with any compoundtypically reactive with hydroxyl groups, providing compounds with newtypes of functionalities. These reactions can utilize an esterificationmechanism following reaction (5), an etherification mechanism followingreactions (6), (7) or (8), or an isocyanate mechanism followingreactions (9) or (10).

Hydroxyl-terminated poly(thioesters) can react using an esterificationmechanism to form compounds of the formula:f ²-R¹—C(O)—[—O-A-O—B—]_(n)—O-A-O—C(O)—R¹-f ²

wherein

A is —((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;

B is —C(O)—R¹—C(O)—;

R¹ is any bi-valenced organic radical;

m is at least zero;

n is at least one;

x is between two and six;

f² is a chemical structure or functional group; and

O, H, C, and S, have their normal meaning of oxygen, hydrogen, carbon,and sulfur.

The esterification reaction takes place in typical conditions for suchreactions, familiar to any person skilled in the art, and is describedin reaction (5).f ²-R¹—C(O)OH+H[—O-A-O—B—]_(n)—O-A-OH+HO(O)C—R¹-f ² →f²-R¹—C(O)—[—O-A-O—B—]_(n)—O-A-O—C(O)—R¹-f ²+2H₂O  (5)

-   where f² is a chemical structure or functional group that introduces    special properties and characteristics, allowing further utilization    of the newly produced compound. The structure of f² includes, but is    not limited to hydroxyl, carboxyl, acrylic, methacrylic, allyl,    vinyl, maleic, activated halogen, nitrile, cyclocarbonate, and    mercaptan.

Examples of carriers of various f² functionalities include:

-   -   For carboxyl functionality—any bi-functional carbonic acids, for        example, maleic or succinic acids, or dimers of fatty acids;    -   For hydroxyl functionality—any compound that has both a hydroxyl        and carboxyl group, for example, glycolic acid;    -   For acrylic functionality—acrylic acid;    -   For methacrylic functionality—methacrylic acid;    -   For active halogen functionality—chloracetic acid, or its        analogs;    -   For allyl, vinyl and other double bond functionalities—any        unsaturated carbonic acid;    -   For maleic double bond functionality—maleic acid;    -   For nitrile functionality—monoesters of any dicarbonic acid and        ethylenecyanohydrin; and    -   For mercaptan functionality—mercaptopropyonic acid.

The case where f² is a carboxyl (i.e. the first reagent in reaction (5)is a dibasic carbonic acid, which can be either the same or differentfrom the dibasic carbonic acid used in the production of the secondreagent in reaction (5)) is of special interest. Introduction of adibasic acid as a second reagent in reaction (5) allows changing themolecular weight of the produced polymer by choosing the structure of R¹and molar ratio of the participants in reaction (5). Any person skilledin the art will recognize that it is possible to produce similarreaction products if, instead of dibasic carbonic acids, the secondreagent in reaction (5) is anhydrides of such acids.

The produced polyesters with poly(thioester) blocks can be used as such,or as additives to other plastics. In the case when thehydroxyl-terminated poly(thioesters) react with maleic acid, theproduced segmented unsaturated polysulfide-containing polyester can becured by all the conventional methods of curing of unsaturatedpolyesters, and used as a copolymerizable additive to the conventionalunsaturated polyesters.

The special properties of hydroxyl groups located in the β-position tothe disulfide group, as taught by the U.S. Pat. No. 2,582,605, allowsthem to easily participate in the reactions of etherification with otheralcohols, glycols and polyols, to form compounds of the formula:R²—[—O-A-O—B—]_(n)—O-A-O—R²

wherein

each R² is R¹-f,

-   -   wherein R¹ is any bi-valenced organic radical, and        -   f is H or any reactive functional group;

each R² is the same or different;

A is —(—(CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;

B is —C(O)—R¹—C(O)—;

-   -   wherein    -   m is at least zero;    -   x is between two and six; and        O, H, C, and S have their normal meaning of oxygen, hydrogen,        carbon, and sulfur.

The etherification reaction takes place in typical conditions for suchreactions, familiar to any person skilled in the art, and is describedin reaction (6).f-R¹—OH+H[—O-A-O—B—]_(n)—O-A-OH+HO—R¹-f→f-R¹—[—O-A-O—B—]_(n)—O-A-O—R¹-f+2H₂O  (6)where f is a chemical structure or functional group that introducesspecial properties and characteristics, allowing further utilization ofthe newly produced compound. The structure of f may be, but is notlimited to hydroxyl, acrylic, methacrylic, allyl, vinyl, maleic,activated halogen, nitrile, cyclocarbonate, mercaptan and amine groups.

Examples of carriers of various f functionalities include:

-   -   For hydroxyl functionality—any diol, polyol, or organic oxide;    -   For acrylic functionality—hydroxy acrylate;    -   For methacrylic functionality—hydroxy methacrylate;    -   For allyl and vinyl functionalities—any compound containing both        a hydroxyl group and an allyl or vinyl group, such as monovinyl        ether of diethyleneglycol;    -   For cyclocarbonate functionality—glycerol carbonate;    -   For amine functionality—N,N′-dialkylethanolamine;    -   For activated halogen functionality—a monoester of any glycol        and chloroacetic acid;    -   For maleic double bond functionality—maleic anhydride;    -   For nitrile functionality—ethylenecyanohydrin; and    -   For mercaptan functionality—mercaptoethanol.

The case where f is a hydroxyl is of a special interest, as it allowschanging the molecular weight of the produced polymer by choosing thestructure of R² and the molar ratio of the participants in the reaction(6).

Another type of etherification reaction takes place when ahydroxyl-terminated poly(thioester) is treated with either ethyleneoxide, or propylene oxide, to form compounds of the formula:H—R⁵—[—O-A-O—B—]_(n)—O-A-R⁶—OH

wherein

A is —((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;

B is —C(O)—R¹—C(O)—;

R¹ is any bi-valenced organic radical;

m is at least zero;

n is at least one;

x is between two and six;

R⁵ is [O—CH₂—CHR³]_(q-k);

R⁶ is [O—CHR³—CH₂]_(q);

R³ is either H or methyl;

q is at least one;

q is greater than or equal to k; and

O, H, C, and S have their normal meaning of oxygen, hydrogen, carbon,and sulfur.

This etherification reaction takes place in typical conditions for suchreactions, familiar to any person skilled in the art, and is describedin reaction (7).

where R³ is either H, or methyl,

q≧1,

q≧k.

This reaction produces derivatives of poly(thioesters) that are useful,for example, in coatings formulations.

Another possible type of useful derivatives of hydroxyl-terminatedpoly(thioesters) can be produced by their reactions with formaldehyde toform polyacetals with a poly(thioester) backbone, as described in thefollowing formula:H—R⁵[—O-A-O—B—]_(n)—O-A-R⁶—OH

wherein

A is —((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;

B is —C(O)—R¹—C(O)—;

R¹ is any bi-valenced organic radical;

m is at least zero;

n is at least one;

x is between two and six;

R⁵ is [O—CHR³]_(q-k);

R⁶ is [O—CHR³]_(k);

R³ is either H or methyl;

q is at least one;

q is greater than or equal to k; and

O, H, C, and S have their normal meaning of oxygen, hydrogen, carbon,and sulfur.

This etherification reaction takes place in typical conditions for suchreactions, familiar to any person skilled in the art, and is describedin reaction (8).qR³CHO+H[—O-A-O—B—]_(n)—O-A-OH→H[O—CHR³]_(q-k)-[—O-A-O—B—]_(n)—O-A-[O—CHR³]_(k)—OH  (8)

The hydroxyl groups of the hydroxyl-terminated poly(thioesters) readilyparticipate in reactions with compounds containing isocyanate groups. Ofthese compounds the most important and frequently used are those madefrom di- and polyisocyanates, of the formula:R³—C(O)—[—O-A-O—B—]_(n)—O-A-O—C(O)—R³

-   -   wherein    -   A is —((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;    -   B is —C(O)—R¹—C(O)—;    -   R¹ is any bi-valenced organic radical;    -   m is at least zero;    -   n is at least one;    -   x is between two and six;    -   R³ is HN— R¹-f³,        -   wherein f³ is a chemical structure of functional group; and    -   O, H, C, S, and N have their normal meaning of oxygen, hydrogen,        carbon, sulfur and nitrogen.

These compounds can be made through the isocyanate reaction shown inreaction (9). This reaction takes place in typical conditions for suchreactions, familiar to any person skilled in the art.f ³-R¹—NCO+H[—O-A-O—B—]_(n)—O-A-OH+OCN—R¹-f ³ →f³-R¹—NH—C(O)—[—O-A-O—B—]_(n)—O-A-O—(O)C—HN—R¹-f ³  (9)where f³ includes, but is not limited to isocyanate, epoxy, acrylic,methacrylic, alkoxysilane, mercaptan, cyclocarbonate, tertiary amine,vinyloxy, and mixtures thereof.

A very important case is when f³ is another isocyanate group. Dependingon the molar ratio between the hydroxyl-terminated poly(thioester) andisocyanate-containing compound, the reaction can either terminate in anisocyanate prepolymer with a poly(thioester) backbone (reaction (10)),or in a polyurethane with polythioester segments.

When hydroxyl-terminated poly(thioester) and isocyanate-containingcompound are taken in the molar ratio close to 1:2, the reactionsbetween them result in the formation of an isocyanate prepolymer of theformula:R³—C(O)—[—O-A-O—B—]_(n)—O-A-O—C(O)—R³

-   -   wherein    -   A is —((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;    -   B is —C(O)—R¹—C(O)—;    -   R¹ is any bi-valenced organic radical;    -   m is at least zero;    -   n is at least one;    -   x is between two and six;    -   R³ is HN—R⁴—NCO,        -   wherein R⁴ is a radical that is located between two            isocyanate groups of a di- or poly-isocyanate; and    -   O, H, C, S, and N have their normal meaning of oxygen, hydrogen,        carbon, sulfur and nitrogen.

This reaction takes place in typical conditions for such reactions,familiar to any person skilled in the art and is described in reaction(10).OCN—R⁴—NCO+H[—O-A-O—B—]_(n)—O-A-OH+OCN—R⁴—NCO→OCN—R⁴—NH—C(O)—[—O-A-O—B—]_(n)—O-A-O—(O)C—HN—R⁴—NCO  (10)where R⁴ is a bivalent radical located between two isocyanate groups ofa diisocyanate, preferably of a diisocyanate with unequal reactivity ofisocyanate groups, such as 2,4-toluene diisocyanate, isophoronediisocyanate, or trimethylhexamethylenediisocyanate.

The isocyanate prepolymers produced by the reaction (10) can be

-   -   a) converted into polyurethanes with poly(thioester) blocks by        reactions with a diol chain extender, and polyol crosslinkers;    -   b) converted into poly(urea-urethanes) with poly(thioester)        blocks by reactions with aromatic diamine chain extenders and        crosslinkers;    -   c) converted into reactive and non-reactive functional oligomers        with poly(thioester) backbones by the methods described in the        U.S. Pat. No. 6,369,188. The functionality of the produced        urethane-functional polysulfide-containing compounds includes,        but is not limited to epoxy, acrylic, methacrylic, alkoxysilane,        mercaptan, cyclocarbonate, tertiary amine, vinyloxy, and        mixtures thereof.

When hydroxyl-terminated poly(thioester) and isocyanate-containingcompound are taken in close-to-equimolar amounts, the reactions betweenthem result in the formation of a polyurethane with polythioestersegments. These polyurethanes have improved properties due to thepresence of polysulfide blocks.

Production of Monomeric (Polythio)Diesters

The present invention also provides monomeric (polythio)diesters of theformula:R⁷—C(O)—O—X—O—C(O)—R⁷

wherein X=—(—(CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;

-   -   R⁷ is either H, or any monovalent organic radical;    -   the two R⁷s are either the same or different;    -   m is at least zero;    -   x is at least one; and        O, H, C, and S have their normal meaning of oxygen, hydrogen,        carbon, and sulfur.

In order to produce these products, dihydroxyethylpolysulfide and/or itshomopolymers react with individual mono-basic carbonic acids, such asacetic, chloroacetic, propyonic, fatty, etc. acids, their anhydrides, ormixtures of such acids or anhydrides under conditions similar to thosedescribed above for dibasic acids. The (polythio)diesters are producedaccording to reaction (11)R⁷—C(O)OH+H[—O-A-O—B—]_(n)—O-A-OH+HO(O)C—R⁷→R⁷—C(O)[—O-A-O—B—]_(n)—O-A-O(O)C—R⁷  (11)where R⁷ is H or any monovalent organic acid. In one embodiment, R⁷ is amonobasic carboxylic acid having between two and nineteen carbons.

The produces low viscosity polysulfide-containing diesters that are veryeffective solvents and plasticizers for a wide variety of polymericproducts.

EXAMPLES

The following examples are offered by way of illustration and not by wayof limitation.

Group a—Examples 1-7 Group A Experimental Group A, Example 1

Production of Carboxyl-Terminated Poly(Thioester) fromDi(Hydroxyethyl)Disulfide and Fatty Acid Dimer

27 g of di(hydroxyethyl)disulfide (DiHEDS, produced by Chevron PhillipsChemical Company LP, Regular grade) and 200 g dimer fatty acid dimer(CAS #61788-89-4, Pripol-1013 from Uniqema, ICI Company) were combinedin a jacketed reaction vessel and agitated. The molar ratio ofcomponents was 1:2.0.2 g (0.05% of the total weight of raw materials) ofp-toluenesulfonic acid monohydrate with 98% purity (CAS number6192-52-5, obtained from Sigma-Aldrich) was used as a catalyst.

The esterification reaction proceeded at 125-130° C. (260-270° F.) for3-4 hours with constant mixing. 10 mm Hg vacuum was applied in order tofacilitate the removal of water from the reaction mixture.

For process control during this stage the concentration of carboxylgroups was monitored by ASTM D 465.

The process ended when the concentration of acid approached thecalculated acid number of the carboxyl-terminated poly(dithioester), andno further distillate was formed. The acid number of the producedmaterial equaled 83.6 mg KOH/g, while the projected acid number was83.58. The produced material was a dark brown liquid with 6000 cPsviscosity.

Group A, Example 2

Production of Hydroxyl-Terminated Poly(Thioester) fromDi(Hydroxyethyl)Disulfide and Succinic Anhydride

308 g Di(hydroxyethyl)disulfide (DiHEDS CP Chem L.L.C., Water-freegrade) and 100 g of succinic anhydride (Sigma-Aldrich #108-30-5) (molarratio 1:2) were combined in a reaction vessel and heated to 120° C.,followed by the addition of 4 g of catalyst, methanesulfonic acid (CASnumber 75-75-2, Sigma-Aldrich). The system was mixed for 1 hr under 10mm Hg vacuum and mixing continued at 120° C. until no more water wasdistilled from the reaction mixture.

For process control the concentration of carboxyl groups was monitoredby ASTM D 465. At the end of the process the residual concentration ofcarboxyl groups was negligible. The produced substance was a clearyellowish viscous (2000 cPs) liquid, which later crystallized into awhite hard waxy material.

Group A, Example 3

Production of Hydroxyl-Terminated Poly(Thioester) fromDi(Hydroxyethyl)Disulfide and Adipic Acid

600 g Di(hydroxyethyl)disulfide (DiHEDS CP Chem L.L.C. Water-free grade)and 474 g of adipic anhydride (Adipure by DuPont, CAS #124-04-9) (molarratio 6:5) were combined in a reaction vessel and 3.13 g ofmethanesulfonic acid (CAS number 75-75-2, Sigma-Aldrich) added. Themixture was heated to 120° C. with mixing for 1 hr, under 10 mm Hgvacuum and reaction maintained at 120° C. until no more water wasdistilled from the reaction mixture.

For process control the concentration of carboxyl groups was monitoredby ASTM D 465. At the end of the process the residual concentration ofcarboxyl groups was negligible.

The produced substance was a clear yellowish viscous (˜3000 cPs) liquid,which later crystallized into a white hard waxy material.

Group A, Example 4

Production of Hydroxyl-Terminated Poly(Thioester) fromDi(Hydroxyethyl)Disulfide, Adipic Acid and Dimethylolpropionic Acid

300 g Di(hydroxyethyl)disulfide (DiHEDS CP Chem L.L.C. Water-freegrade), 426 g of adipic acid, and 196 g of DMPA (GEO SpecialtyChemicals, CAS #4767-03-7) (molar ratio 4:6:3) were combined and heatedat 160° C. with mixing for 2.5 hr, under 10 mm Hg vacuum. Thetemperature was increased to 180° C., and mixing continued at 180° C.until no more water was distilled from the reaction mixture.

The concentration of carboxyl groups was monitored by ASTM D 465. At theend of the process the residual concentration of carboxyl groups wasequal to the concentration of the DMPA carboxyls.

The produced material was an amber highly viscous (200,000 cPs) liquid.

Group A, Example 5

Production of Polysulfide-Containing Amidoamine from theCarboxyl-Terminated Poly(Thioester)

To the product from the Example 1 without isolation or cooling was addedN-aminoethylpiperazine (AEP, CAS #140-31-8, Huntsman Corp. or AirProducts and Chemicals, Inc.) in the amount of 1.05 mol AEP per one molof carboxyl. Assuming the targeted acid number of 83.58 mg KOH/g wasreached in the first stage, the ratio is 20.4 parts of AEP per 100 partsof produced polyester.

A typical second stage reaction time is 2-3 hours at 155-160° C. underatmospheric pressure. After reaching the targeted amine number, whichfor this product is 71.2 mg KOH/g, the reactor pressure was reduced toat least 10 mm Hg to distill off the water produced in the second stagereaction. The temperature during the vacuum period is maintained at155-160° C.

For process control in this stage the amine number is monitored by ASTMD 2073. The process ends when the amine number approaches the targetedamine number and no more water was being removed under vacuum.

The produced material was a brown semi-solid substance with a meltingrange 40-50° C. that was soluble in conventional amidoamines andphenylalkylamines.

Group A, Example 6

Production of Polysulfide-Containing Isocyanate Prepolymer with TerminalIsocyanate Groups from Hydroxyl-Terminated Poly(Thioester)

400 g of poly(thioester) from Example 2 were melted at 60° C. and mixedwith 15 g 3ST Zeochem Purmol Zeolite powder (produced by Zeochem,Louisville, Ky.) to remove traces of water. The mixture was latercombined in a reaction vessel with 234 g of isophorone diisocyanate(Vestanat® IPDI, Degussa Corp., CAS #4098-71-9) (molar ratio 1:2.05).The reaction mixture was heated to 90° C. and agitated for 3 hrs underargon flow.

The concentration of isocyanate groups was monitored by ASTM D 2572-97.At the end of the process the concentration of isocyanate groups was 2.4N, which is equal to half of the initial concentration of isocyanategroups.

The produced material was a whitish opaque very viscous (150,000 cPs)liquid.

Group A, Example 7

Production of Polysulfide-Containing Isocyanate Prepolymer fromHydroxyl-Terminated Poly(Thioester)

445 g of poly(thioester) from Example 3 were melted at 60° C. and mixedwith 15 g 3ST Zeochem Purmol Zeolite powder (produced by Zeochem,Louisville, Ky.) to remove traces of water. The produced mixture wascombined in a reaction vessel with 372 g ofmethylene-bis(4-cyclohexylisocyanate) (Desmodur W, Bayer Corp., CAS#5124-30-1) and heated to 90° C. and stirred for 1 hr, under argon flow.95.2 g of dimethylolpropionic acid (DMPA, GEO Specialty Chemicals, CAS#4767-03-7), 200 g of N-methyl pyrrolidinone (NMP BASF, CAS #872-50-4)and 36 g of triethylamine (TEA, JT Baker, CAS #121-44-8) were added tothe reaction mixture. The temperature was reduced to 70° C. and thereaction mixture was mixed at this temperature for 1 hour under argon.

The concentration of isocyanate groups was monitored by ASTM D 2572-97.At the end of the process the concentration of isocyanate groups was0.68 N, which exactly equaled the calculated concentration of terminalisocyanate groups in the produced prepolymer with pendant carboxylgroups inhibited from reaction by the triethylamine.

The produced material was a whitish viscous liquid with viscosity ofapproximately 70,000 cPs.

It is evident from the above results that the subject compounds can bereadily prepared in good yield under convenient conditions. The subjectmonomers provide desirable properties to a large number of productsenhancing the properties of products prepared from conventionalmonomers. By replacing all or a portion of diols or dibasic acids usedin making condensation polymers, the resulting products have improvedphysical and chemical characteristics. By modifying the subject monomerswith addition polymerizable monomers, the properties of the resultingpolymeric product are similarly enhanced.

Group B—Examples 1-7 Group B Experimental

The majority of experimental work on the products described in thispatent was based on a commercially-available DiHEDS, a product of theChevron Phillips Chemicals LP, which contains approximately 95-97% ofdi(hydroxyethyl)disulfide, and 3-5% of the higher molecular weightdi(hydroxyethyl)trisulfide and other, higher molecular weightdi(hydroxyethyl)polysulfides. However, in regards to the subject of thisinvention, all di(hydroxyethyl)polysulfides behave similarly.

Di(hydroxyethyl)polysulfides with sulfidity higher than that of DiHEDS,which were used to create some of the poly(thioesters) that are thesubject of this invention, were obtained by dissolving elemental sulfurin DiHEDS at 115-120° C.

The homopolymers of di(hydroxyethyl)polysulfides (polythioethers) thatwere used to create some of the poly(thioesters) that are the subject ofthis invention were obtained by polyetherification of DiHEDS(Reaction 1) in the presence of acidic catalysts (preferably phosphoricacid) at 140-180° C.

Any person skilled in the art will recognize that most of the processesdescribed in the present invention can take place not only at 80-130°C., in the presence of acidic catalysts, but also outside of thispreferred range of temperatures. However, at temperatures below 80° C.the reaction rate slows down to a degree that the chemical productionprocess becomes impractical, and at temperatures above 130° C. the inputof the reaction of homopolycondensation of di(hydroxyethyl)polysulfides(i.e. formation of poly(thioethers)) becomes more and more pronounced,and the determination of the chemical structure of the products formedat higher temperatures becomes more and more problematic. An exceptionis when the reaction is conducted with methanesulphonic acid as thecatalyst. In this case, the homopolycondensation reaction is minimal upto about 180° C.

Group B, Example 1

Production of Carboxyl-Terminated Poly(Thioester) fromDi(Hydroxyethyl)Disulfide and Fatty Acid Dimer

27 g of di(hydroxyethyl)disulfide (DiHEDS, produced by Chevron PhillipsChemicals LP, Regular grade) and 200 g fatty acid dimer (CAS#61788-89-4, Pripol-1013 from Uniqema, ICI Company) were combined in ajacketed reaction vessel and agitated. The molar ratio of components was1:2.

0.2 g of 98% p-toluenesulfonic acid monohydrate (CAS #6192-52-5,obtained from Sigma-Aldrich) was used as a catalyst. The esterificationreaction proceeded at 125-130° C. (260-270° F.) for 3-4 hours withconstant mixing. 10 mm Hg vacuum was applied in order to facilitate theremoval of water from the reaction mixture. For process control duringthis stage the concentration of carboxyl groups was monitored (ASTM D465).

The process ended when the concentration of acid approached thecalculated acid number of the carboxyl-terminated polythioester, and nofurther distillate was formed. The acid number of the produced materialequaled 83.6 mg KOH/g, while the projected acid number was 83.58. Thematerial produced was a brown liquid with 6000 cPs viscosity.

Group B, Example 2

Production of Hydroxyl-Terminated Poly(Thioester) fromDi(Hydroxyethyl)Disulfide and Succinic Anhydride

308 g di(hydroxyethyl)disulfide (DiHEDS, CPChem L.L.C., Water-freegrade) and 100 g of succinic anhydride (Sigma-Aldrich #108-30-5) (molarratio 1:2) were combined in a reaction vessel and heated to 120° C.,followed by the addition of 4 g of catalyst, methanesulfonic acid (CAS#75-75-2, Sigma-Aldrich). The system was mixed for 1 hr under 10 mm Hgvacuum and mixing continued at 120° C. until no more water was distilledfrom the reaction mixture. For process control the concentration ofcarboxyl groups was monitored by ASTM D 465. At the end of the processthe residual concentration of carboxyl groups was negligible. Theproduced substance was a clear yellowish viscous (2000 cPs) liquid,which later crystallized into a white hard waxy material.

Group B, Example 3

Production of Hydroxyl-Terminated Poly(Thioester) fromDi(Hydroxyethyl)Disulfide and Adipic Acid

600 g di(hydroxyethyl)disulfide (DiHEDS, CP Chem L.L.C. Water-freegrade) and 474 g of adipic acid (Adipure by DuPont, CAS #124-04-9)(molar ratio 6:5) were combined in a reaction vessel and 3.13 g ofmethanesulfonic acid (CAS number 75-75-2, Sigma-Aldrich) added. Themixture was heated to 120° C. with mixing for 1 hr, under 10 mm Hgvacuum and reaction maintained at 120° C. until no more water wasdistilled from the reaction mixture. For process control theconcentration of carboxyl groups was monitored by ASTM D 465. At the endof the process the residual concentration of carboxyl groups wasnegligible. The produced substance was a clear yellowish viscous (˜3000cPs) liquid, which later crystallized into a white hard waxy material.

Group B, Example 4

Production of Hydroxyl-Terminated Poly(Thioester) fromDi(Hydroxyethyl)Disulfide and Maleic Anhydride

1900 g di(hydroxyethyl)disulfide (DiHEDS CP Chem L.L.C. Water-freegrade) and 907 g of maleic anhydride (Alfa Aesar, CAS #108-31-6) (molarratio 4:3) were combined in a reaction vessel. The mixture was heated to57° C. with mixing for 1 hr, under Argon, until maleic anhydridedissolved. The reaction mixture was intensely agitated for 40 minuteswithout external heat source, and the temperature has ridden to 80° C.14 g of methanesulfonic acid (Chevron Phillips Chemicals, CAS number75-75-2) were added and the mixture was heated to 90° C. for 10 minutes.Argon was turned off when the condensation products were observed on thewalls of the reactor, and 10 mm Hg vacuum was applied for 1 hour at 80°C., until no more water was distilled from the reaction mixture. Forprocess control the concentration of carboxyl groups was monitored byFTIR. At the end of the process the residual concentration of carboxylgroups was negligible (the peaks 1785 and 1850 cm¹ attributed to themaleic anhydride and 1705 cm¹ attributed to the carboxyl's carbonylgroup have disappeared). The produced substance was a clear not veryviscous (˜800 cPs) liquid.

The spectrum of this product is shown in FIG. 1 alongside with aspectrum of a material produced from the same raw materials underconditions described by Weihe (U.S. Pat. No. 2,221,418, Example4—equimolar amounts, 5 hours @140° C.), which is an extremely viscous(>500,000 cPs) dark brown balsam. These spectra clearly demonstrate thatthe compositions of matter generated from the same raw materials underdifferent conditions are quite dissimilar. Similar spectral differencesare present in the products of interaction of succinic anhydride anddi(hydroxyethyl)disulfide when they were obtained under conditionsdescribed by Smith (180-220° F. in the presence of triethylamine).

Group B, Example 5

Production of Hydroxyl-Terminated Poly(Thioester) fromDi(Hydroxyethyl)Disulfide, Succinic Anhydride and DimethylolpropionicAcid

308 g di(hydroxyethyl)disulfide (DiHEDS CP Chem L.L.C. Water-freegrade), 400 g of succinic anhydride, and 402 g of dimethylolpropionicacid (DMPA, GEO Specialty Chemicals, CAS #4767-03-7) (molar ratio 2:4:3)were combined and heated to 130° C. with mixing for 2.5 hr, under 10 mmHg vacuum. Under these conditions, all hydroxyls of DiHEDS have reactedwith the carboxyl groups of the succinic acid, forming acarboxyl-terminated polythioester dissolved in the residualdimethylolpropionic and succinic acids.

Then the temperature was increased to 180° C., 1% of methanesulphonicacid catalyst was added to the reaction mixture, and mixing continued at180° C. until no more water was distilled from the reaction mixture. Atthis stage of the process, dimethylolpropionic acid, acting as a diol,has reacted with the residual succinic acid and carboxyl-terminatedpolythioester, forming an oligomeric resin with a polythioester backbonethat is terminated with two hydroxyl and three carboxyl groups.

The concentration of carboxyl groups was monitored by ASTM D 465. At theend of the process the residual concentration of carboxyl groups wasequal to the concentration of the DMPA carboxyls. The produced materialwas an amber highly viscous (200,000 cPs) liquid.

Group B, Example 6

Production of Polysulfide-Containing Amidoamine from theCarboxyl-Terminated Poly(Thioester)

To the product from the Example 1 without isolation or cooling was addedN-aminoethylpiperazine (AEP, CAS #140-31-8, Huntsman Corp. or AirProducts and Chemicals, Inc) in the amount of 1.05 mol AEP per one molof carboxyl. Assuming the targeted acid number of 83.58 mg KOH/g wasreached in the first stage, the ratio is 20.4 parts of AEP per 100 partsof produced polyester. A typical second stage reaction time is 2-3 hoursat 155-160° C. under atmospheric pressure. After reaching the targetedamine number, which for this product is 71.2 mg KOH/g, the reactorpressure was reduced to at least 10 mm Hg. to distill off the waterproduced in the second stage reaction. The temperature during the vacuumperiod is maintained at 155-160° C. For process control in this stagethe amine number is monitored by ASTM D 2073. The process ends when theamine number approaches the targeted amine number and no more water wasbeing removed under vacuum. The produced material was a brown semi-solidsubstance with a melting range 40-50° C. that was soluble inconventional diamines.

Group B, Example 7

Production of Polysulfide-Containing Isocyanate Prepolymer fromHydroxyl-Terminated Poly(Thioester)

400 g of poly(thioester) from Example 2 were melted at 60° C. and mixedwith 15 g 3ST 25 Zeochem Purmol Zeolite powder (produced by Zeochem,Louisville, Ky.) to remove traces of water. The mixture was latercombined in a reaction vessel with 234 g of isophorone diisocyanate(Vestanat® IPDI, Degussa Corp., CAS #4098-71-9) (molar ratio 1:2.05).The reaction mixture was heated to 90° C. and agitated for 3 hrs underargon flow. The concentration of isocyanate groups was monitored by ASTMD 2572-97. At the end of the process the concentration of isocyanategroups was 2.4 N, which is equal to half of the initial concentration ofisocyanate groups. The produced material was a whitish opaque veryviscous (150,000 cPs) liquid.

Group B, Example 8

Production of Polysulfide-Containing Isocyanate Prepolymer fromHydroxyl-Terminated Poly(Thioester)

445 g of poly(thioester) from Example 3 were melted at 60° C. and mixedwith 15 g 3ST Zeochem Purmol Zeolite powder (produced by Zeochem,Louisville, Ky.) to remove traces of water. The produced mixture wascombined in a reaction vessel with 372 g ofmethylene-bis(cyclohexylisocyanate) (Desmodur W, Bayer Corp., CAS#5124-30-1) and heated to 90° C. and stirred for 1 hr, under argon flow.

95.2 g of dimethylolpropionic acid (DMPA, GEO Specialty Chemicals, CAS#4767-03-7), 200 g of N-methyl pyrrolidinone (NMP BASF, CAS #872-50-4)and 36 g of triethylamine (TEA, JT Baker, CAS #121-44-8) were added tothe reaction mixture. The temperature was reduced to 70° C. and thereaction mixture was mixed at this temperature for 1 hour under argon.The concentration of isocyanate groups was monitored by ASTM D 2572-97.At the end of the process the concentration of isocyanate groups was0.68 N, which exactly equaled the calculated concentration of terminalisocyanate groups in the produced prepolymer with pendant carboxylgroups inhibited from reaction by the triethylamine. The producedmaterial was a whitish viscous liquid with viscosity of approximately70,000 cPs.

Group B, Example 9

Production of Hydroxyl-Terminated Poly(Thioester) fromDi(Hydroxyethyl)Polysulfide and Adipic Acid

504 g of di(hydroxyethyl)polysulfide (obtained by dissolving 1 mol ofsulfur in 1 mol of DiHEDS) and 313 g of adipic acid (Adipure by DuPont,CAS #124-04-9) (molar ratio 5:4) were combined in a reaction vessel and3 g of 70% solution of methanesulfonic acid (produced by ChevronPhillips Chemical) were added to the reaction mixture. The mixture washeated to 120° C. with mixing for 1 hr, under 10 mm Hg vacuum andreaction maintained at 120° C. until no more water was distilled fromthe reaction mixture. For process control the concentration of carboxylgroups was monitored by ASTM D 465. At the end of the process theresidual concentration of carboxyl groups was negligible. The producedsubstance was a brown viscous liquid, which did not crystallize. Thespectrum of this material is shown in FIG. 2.

By way of comparison, di(hydroxyethyl)disulfide (a compound excluded byWilson from the list of sulfur-containing diols) and adipic acid werecombined under conditions described by Wilson (180° C., nitrogenatmosphere followed by vacuum, lead acetate/antimony oxide catalyst).The spectrum of the resulting materials is shown in FIG. 2, alongsidewith a spectrum of the inventive product. The resulting polymers provedto have absolutely dissimilar structures.

Group B, Example 10

Production of the Maleic-Terminated Polythioester withDi(Hydroxyethyl)Polysulfide/Adipic Acid Polyester Backbone

673 g of poly(thioester) from Example 9 were combined with 105 g ofmaleic anhydride. and heated to 90° C. with stirring under argon, untilFTIR spectrum has shown complete disappearance of the peaks 1785 and1850 cm⁻¹ attributed to the anhydride group of maleic anhydride.

The produced material was a whitish viscous liquid with viscosity ofapproximately 10,000 cPs, which demonstrated the typical reactions ofmaleic-terminated oligomers.

Group B, Example 11

Production of Carboxyl-Terminated Poly(Thioester) fromDi(Hydroxyethyl)Polysulfide and Adipic Acid

452 g of di(hydroxyethyl)polysulfide (obtained by dissolving 1 mol ofsulfur in 1 mol of DiHEDS) and 532 g of adipic acid (Adipure by DuPont,CAS #124-04-9) (molar ratio 2:3) were combined in a reaction vessel and5.3 g of 70% solution of methanesulfonic acid (produced by ChevronPhillips Chemical) were added to the reaction mixture. The mixture washeated to 115° C. with mixing for 1 hr, under 10 mm Hg vacuum andreaction maintained at 115° C. until no more water was distilled fromthe reaction mixture. For process control the concentration of carboxylgroups was monitored by ASTM D 465. At the end of the process the molarconcentration of carboxyl groups was 2.8, while theoretically it shouldbe 2.71. The produced substance was a brown viscous liquid, which didnot crystallize.

Group B, Example 12

Production of the Mercaptan-Terminated Polythioester withDi(Hydroxyethyl)Polysulfide/Adipic Acid Polyester Backbone

900 g of poly(thioester) from Example 11 were combined with 190 g ofbis-mercaptoethanol (BME, produced by Chevron Phillips Chemical).Additional 2.3 g of 70% solution of methanesulfonic acid (produced byChevron Phillips Chemical) were added to the reaction mixture, which washeated to 90° C. with stirring under argon for 1 hour. Then 10 mm Hgvacuum was applied and reaction maintained at 90° C. until no moredistillate was produced, and until FTIR spectrum has shown completedisappearance of the 1705 cm¹ peak, which is attributed to thecarboxyl's carbonyl group.

The produced material was a brow viscous liquid with viscosity ofapproximately 10,000 cPs, which demonstrated the typical reactions ofmercaptan-terminated oligomers.

Group B, Example 13

Production of a Monomeric Diester from Di(Hydroxyethyl)Disulfide andAcetic Acid

154 g di(hydroxyethyl)disulfide (DiHEDS CPChem L.L.C., Water-free grade)and 120 g of glacial acetic acid (molar ratio 1:2) were combined in areaction vessel and heated to 75° C., followed by the addition of 0.85 gof catalyst, methanesulfonic acid (CAS number 75-75-2, Sigma-Aldrich).The system was heating to 90° C. and mixed for 1 hr. The temperature wasraised to 103° C. and 10 mm Hg vacuum was applied. The system cooleddown to 75° C., and extra 50 g of glacial acetic acid were added. Thereaction mixture was reheated, and vacuum was applied. This operation(including the addition of extra portions of acetic acid) was repeated 3times, until changes in the FTIR spectrum after each reheating cyclebecame unnoticeable. The produced substance was a clear low viscosityliquid with specific gravity 1.21-1.22, which was a very effectiveplasticizer for a wide variety of halogenated polymers.

It is evident from the above results that the subject compounds can bereadily prepared in good yield under convenient conditions. The subjectmonomers provide desirable properties to a large number of productsenhancing the properties of products prepared from conventionalmonomers. By replacing all or a portion of diols or dibasic acids usedin making condensation polymers, the resulting products have improvedphysical and chemical characteristics. By modifying the subject monomerswith addition polymerizable monomers, the properties of the resultingpolymeric product are similarly enhanced.

The references, articles, patent applications and patents, describedthroughout this specification are fully incorporated by reference, as iffully disclosed in their entirety herein.

Having now fully described the invention, it will be apparent to one ofordinary skill in the art that many changes and modifications can bemade thereto without departing from the spirit or scope of the inventionas set forth herein.

As one of ordinary skill in the art will appreciate, various changes,substitutions, and alterations could be made or otherwise implementedwithout departing from the principles of the present invention.Accordingly, the scope of the invention should be determined by thefollowing claims and their legal equivalents.

Specific Embodiments

The following are nonlimiting, specific embodiments in accordance withthe present disclosure:

1. A compound characterized by having a unit formed from a polysulfidediol and an organic dibasic carboxylic acid or its anhydride, whereinthe hydroxyl groups are separated from said polysulfide by at least 2carbon atoms, having a total of at least about 5 carbon atoms, saidpolysulfide having from 2 to 8 sulfur atoms.

2. A compound according to embodiment 1, wherein said dibasic acid is anorganic dicarboxylic acid or anhydride of at least about 2 carbon atomsand said polysulfide diol is aliphatic of from 4 to 40 carbon atoms.

3. A compound according to embodiment 2, wherein said polysulfide hasfrom 2 to 4 sulfur atoms.

4. A compound according to embodiment 1, wherein said compound is acondensation copolymer.

5. A compound according to embodiment 1, wherein said compound is anaddition polymer.

6. A compound having at least one unit of the formula:—ORS_(n)R¹OA- or —OAORS_(n)R¹—wherein:

O and S have their normal meaning of oxygen and sulfur;

n is at least 2 and not more than about 8;

R and R¹ are the same or different and are organic divalent radicals,each having from 2 to 20 carbon atoms; and

A is the residue of a dibasic carboxylic acid of from 1 to 40 carbonatoms.

7. A composition of the formulae:MF_(m)ORS_(n)R¹OM¹; or  (a)MZAORS_(n)R¹F¹ _(m)OAZ¹M¹,  (b)wherein

O and S have their normal meaning of oxygen and sulfur;

n is at least 2 and not more than about 8;

F is of the formula —ORS_(n)R¹OA-;

F¹ is of the formula —OAORS_(n)R¹—

m is at least 1;

Z and Z¹ are the same or different and are oxy or amino;

M and M¹ are the same or different and are hydrogen or an organicsubstituent;

R and R¹ are the same or different and are organic divalent radicals,each having from 2 to 20 carbon atoms; and

A is the residue of a dicarboxylic acid of from 2 to 40 carbon atoms.

8. A composition according to embodiment 7, wherein M and M¹ arehydrogen and A is of from 2 to 12 carbon atoms and R and R¹ arealiphatic.

9. A composition according to embodiment 7, wherein A is a fatty aciddimer residue and R and R¹ are aliphatic.

10. A composition according to embodiment 7, wherein:

M is defined as WR²—; and

M¹ is defined as W¹R³—,

wherein:

R² and R³ are the same or different and are an organic divalent radicalhaving from 2 to 12 carbon atoms; and

W and W¹ are the same or different, and are amino and substituted aminoof from about 1 to 6 carbon atoms, hydroxyl, carboxyl, isothiocyanate,isocyanate, oxo-carbonyl, non-oxo-carbonyl, siloxane, silane,cyclocarbonate, active olefin, or active halogen.

11. A copolymer comprising as a monomer a composition according toembodiment 7 wherein:

said organic substituent for M is defined as WR²— and for M¹ as W¹R³;

R² and R³ are the same or different and are an organic divalent radicalhaving from 2 to 12 carbon atoms; and

W and W¹ are the same or different, and are amino and substituted aminoof from about 1 to 6 carbon atoms, hydroxyl, carboxyl, isothiocyanate,isocyanate, oxo-carbonyl, non-oxo-carbonyl, siloxane, cyclocarbonate,active olefin, or active halogen.

12. A compound according to embodiment 11, wherein said polymer is apolyurethane.

13. A compound according to embodiment 11, wherein said polymer is apolyether.

14. A compound according to embodiment 11, wherein said polymer is apolyester.

15. A compound according to embodiment 11, wherein said polymer is anaddition polymer.

16. A copolymer according to embodiment 11, wherein A is a dicarboxylicacid residue of from 2 to 8 carbon atoms and n is 2 to 4.

17. A compound according to embodiment 15, wherein at least one of W andW¹ is hydroxyl.

18. A compound according to embodiment 15, wherein at least one of W andW¹ is carboxyl.

19. A compound according to embodiment 15, wherein at least one of W andW¹ is an amine.

20. A compound of the formulae:MF_(m)ORS_(n)R¹OM¹; or  (a)MF¹ _(m)OAOM¹,  (b)wherein:

F is of the formula —ORS_(n)R¹OA-;

F¹ is of the formula —OAORS_(n)R¹—;

m is at least 1;

n is of 2 to 4;

R and R¹ are ethylene;

A is the residue of an aliphatic dicarboxylic acid of from 2 to 40carbon atoms; and

M and M¹ are H.

21. A composition resulting from the reaction of the reactantsdi(hydroxyethyl)disulfide, succinic or adipic acid anddimethylolpropionic acid and an acid catalyst.

22. An object of a polymer comprising a compound according to embodiment1.

23. A compound of the formula:R²—[—O-A-O—B—]_(n)—O-A-O—R²

-   -   wherein    -   each R² is H or R¹-f,        -   wherein R¹ is any bi-valenced organic radical, and            -   f is H or any reactive functional group;    -   each R² is the same or different;    -   A is either X or Y,        -   wherein X is            —(—(CH₂)₂—S_(x)—(CH₂)₂O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—,            -   Y is —C(O)—R¹—C(O)—,            -   m is at least zero, and            -   x is between two and six;    -   B is either Y or X;    -   O, H, C, and S have their normal meaning of oxygen, hydrogen,        carbon, and sulfur;    -   if A is X, then B is Y;    -   if A is Y, then B is X; and    -   n is at least one, except for the case when A is Y, B is X, R¹        is a dibasic carbonic acid that is a cyclic anhydride or forms a        cyclic anhydride, and R² is H, in which case n is at least two.

24. The compound as set forth in embodiment 23, wherein

-   -   R² is R¹-f;    -   A is —C(O)—R¹—C(O)—; and    -   B is —(—(CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—.

25. The compound as set forth in embodiment 23, wherein

-   -   R² is R¹-f;    -   A is —(—(CH₂)₂—S_(x)—(CH₂)₂O—)_(m)—(CH₂)₂—₂-S—(CH₂)₂—; and    -   B is —C(O)—R¹—C(O)—.

26. The compound as set forth in embodiment 23, wherein

-   -   f is selected from the group consisting of hydroxyl, acrylic,        methacrylic, allyl, vinyl, maleic, activated halogen, nitrile,        cyclocarbonate, mercaptan, and amine groups.

27. A composition comprising the compound as set forth in embodiment 23.

28. The composition as set forth in embodiment 27, wherein saidcomposition is selected from the group consisting of adhesives,sealants, caulks, coatings, paints, plastics, and elastomers.

29. A compound produced from the reaction between

-   -   a) di(hydroxyethyl)polysulfides, homopolymers of        di(hydroxyethyl)polysulfides, or a mixture of        di(hydroxyethyl)polysulfides and homopolomyers of        di(hydroxyethyl)polysulfides; and    -   b) mono-basic or di-basic carbonic acids, their anhydrides,        mixtures of dibasic carbonic acids and their anhydrides, or        mixtures of mono-basic carbonic acids and their anhydrides;        -   wherein said reaction is conducted at a temperature of            between about 80° C. and about 130° C., and wherein said            reaction is conducted in the presence of a protonic acidic            catalyst.

30. The compound as set forth in embodiment 29, wherein said acidiccatalyst comprises a nonoxidizing acidic catalyst.

31. The compound as set forth in embodiment 29, wherein saidnonoxidizing acidic catalyst comprises methanesulphonic acid.

32. The compound as set forth in embodiment 29, wherein said carbonicacids and their anhydrides are selected from the group consisting ofC₂-C₄₀ saturated and unsaturated carbonic acids, substituted andunsubstituted carboxylic mono- and diacids and their anhydrides.

33. The compound as set forth in embodiment 29, wherein saiddi(hydroxyethyl) polysulfides are selected from the group consisting ofdi(hydroxyethyl)disulfide, di(hydroxyethyl)trisulfide anddi(hydroxyethyl)tetrasulfide.

34. A compound produced from the reaction between

-   -   a) di(hidroxyethyl)polysulfides, homopolymers of        di(hydroxyethyl)polysulfides, or a mixture of        di(hydroxyethyl)polysulfides and homopolomyers of        di(hydroxyethyl)polysulfides; and    -   b) mono-basic or di-basic carbonic acids, their anhydrides,        mixtures of dibasic carbonic acids and their anhydrides, or        mixtures of mono-basic carbonic acids and their anhydrides;    -   wherein said reaction is conducted at a temperature of between        about 80° C. and about 180° C., and wherein said reaction is        conducted in the presence of methanesulphonic acid.

35. The compound as set forth in embodiment 34, wherein said carbonicacids and their anhydrides are selected from the group consisting ofC₂-C₄₀ saturated and unsaturated carbonic acids, substituted andunsubstituted carboxylic mono- and diacids and their anhydrides.

36. The compound as set forth in embodiment 34, wherein saiddi(hydroxyethyl) polysulfides are selected from the group consisting ofdi(hydroxyethyl)disulfide, di(hydroxyethyl)trisulfide anddi(hydroxyethyl)tetrasulfide.

37. A compound of the formula:f ¹-R¹—NH-A-O—B—[—O-A-O—B—]_(n)—O-A-HN—R¹-f ¹wherein

-   -   A is —C(O)—R¹—C(O)—;    -   B is —((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;    -   R¹ is any bi-valenced organic radical;    -   m is at least zero;    -   n is at least one;    -   x is between two and six;    -   f¹ is a hydroxyl, a primary amine group, a secondary amine group        or a tertiary amine group; and    -   O, H, C, S, and N have their normal meaning of oxygen, hydrogen,        carbon, sulfur and nitrogen.

38. A compound of the formula:R³—C(O)—[—O-A-O—B—]_(n)—O-A-O—C(O)—R³wherein

-   -   A is —((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;    -   B is —C(O)—R¹—C(O)—;    -   R¹ is any bi-valenced organic radical;    -   m is at least zero;    -   n is at least one;    -   x is between two and six;    -   R³ is R¹-f², HN— R¹-f³, or HN—R⁴—NCO,    -   wherein f² is a chemical structure or functional group;    -   f³ is a chemical structure of functional group; and    -   R⁴ is a radical that is located between two isocyanate groups of        a di- or poly-isocyanate; and    -   O, H, C, S, and N have their normal meaning of oxygen, hydrogen,        carbon, sulfur and nitrogen.

39. The compound as set forth in embodiment 38, wherein f² is selectedfrom the group consisting of hydroxyl, carboxyl, acrylic, methacrylic,allyl, vinyl, maleic, activated halogen, nitrile, cyclocarbonate,mercaptan, and tertiary amine groups.

40. The compound a set forth in embodiment 38, wherein f³ is selectedfrom the group consisting of isocyanate, epoxy, acrylic, methacrylic,alkoxysilane, tertiary amine, cyclocarbonate, mercaptan and vinyloxy.

41. A compound of the formula:H—R⁵—[—O-A-O—B—]_(n)—O-A-R⁶—OH

wherein

A is —((CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—((CH₂)₂—S_(x)—(CH₂)₂—;

B is —C(O)—R¹—C(O)—;

R¹ is any bi-valenced organic radical;

m is at least zero;

n is at least one;

x is between two and six;

R⁵ is [O—CH₂—CHR³]_(q-k) or [O—CHR³]_(q-k);

R⁶ is [O—CHR³—CH₂]_(q) or [O—CHR³]_(k);

if R⁵ is [O—CH₂—CHR³]_(q-k), then R⁶ is [O—CHR³—CH₂]_(q);

if R⁵ is [O—CHR³]_(q-k), then R⁶ is [O—CHR³]_(k);

R³ is either H or methyl;

q is at least one;

q is greater than or equal to k; and

O, H, C, and S have their normal meaning of oxygen, hydrogen, carbon,and sulfur.

42. A compound of the formula:R⁷—C(O)—O—X—O—C(O)—R⁷

wherein X=—(—(CH₂)₂—S_(x)—(CH₂)₂—O—)_(m)—(CH₂)₂—S_(x)—(CH₂)₂—;

-   -   R⁷ is either H, or any monovalent organic radical;    -   each R⁷ is the same or different;    -   m is at least zero;    -   x is at least one; and    -   O, H, C, and S have their normal meaning of oxygen, hydrogen,        carbon, and sulfur.

43. The compound as set forth in embodiment 42, wherein R⁷ is amonobasic carboxylic acid having between two and nineteen carbons.

What is claimed is:
 1. A composition of the formulae:MF_(m)ORS_(n)R¹OM¹ wherein: O and S have their normal meaning of oxygenand sulfur; n is at least 2 and, not more than 8; F is of the formula—ORS_(n)R¹OA-; m is at least 1; M and M¹ are the same or different andare hydrogen or an organic substituent; R and R¹ are the same ordifferent and are organic divalent radicals, each having from 2 to 20carbon atoms; and A is the residue of a dicarboxylic acid of from 2 to40 carbon atoms.
 2. A composition according to claim 1, wherein M and M¹are hydrogen, and A is of from 2 to 12 carbon atoms, and R and R¹ arealiphatic.
 3. A composition according to claim 1, wherein M and M¹ arehydrogen, A is a fatty acid dimer residue, and R and R¹ are aliphatic.4. A composition according to claim 1, wherein M and M¹ are hydrogen, nis 2 to 4, R and R¹ are ethylene, and A is a fatty acid dimer residue.5. A composition according to claim 1, wherein: M is defined as WR²— andM¹ is defined as W¹R³—, wherein: R² and R³ are the same or different andare an organic divalent radical having from 2 to 12 carbon atoms; and Wand W¹ are the same or different, and are amino and substituted amino offrom 1 to 6 carbon atoms, hydroxyl, carboxyl, isothiocyanate,oxo-carbonyl, non-oxo-carbonyl, siloxane, cyclocarbonate, active olefin,or active hydrogen.
 6. A composition according to claim 5, wherein A isof from 2 to 12 carbon atoms, R and R¹ are aliphatic.
 7. A compositionaccording to claim 5, wherein A is a fatty acid dimer residue, and R andR¹ are aliphatic.
 8. A composition according to claim 5, wherein n is 2to 4, R and R¹ are ethylene, and A is a fatty acid dimer residue.
 9. Acopolymer comprising as a monomer a composition according to claim 5,wherein: said organic substituent for M is defined as WR²—; M¹ isdefined as W¹R³—; R² and R³ are the same or different and are an organicdivalent radical having from 2 to 12 carbon atoms; and W and W¹ are thesame or different, and are amino and substituted amino of from about 1to 6 carbon atoms, hydroxyl, carboxyl, isothiocyanate, isocyanate,oxocarbonyl, non-oxocarbonyl, siloxane, silane, cyclocarbonate, activeolefin, or active halogen.
 10. A copolymer according to claim 9, whereinsaid copolymer is a polyurethane.
 11. A copolymer according to claim 9,wherein said copolymer is a polyether.
 12. A copolymer according toclaim 9, wherein said copolymer is a polyester.
 13. A copolymeraccording to claim 9, wherein said copolymer is an addition polymer. 14.A copolymer according to claim 9, wherein A is a dicarboxylic acidresidue of from 2 to 8 carbon atoms and n is 2 to
 4. 15. A copolymeraccording to claim 14, wherein at least one of W and W¹ is hydroxyl. 16.A copolymer according to claim 14, wherein at least one of W and W¹ iscarboxyl.
 17. A copolymer according to claim 14, wherein at least one ofW and W¹ is an amine.
 18. A copolymer according to claim 9, wherein A isfrom 2 to 12 carbon atoms, R and R¹ are aliphatic.
 19. A copolymeraccording to claim 9, wherein A is a fatty acid dimer residue, and R andR¹ are aliphatic.
 20. A copolymer according to claim 9, wherein n is 2to 4, R and R¹ are ethylene, and A is a fatty acid dimer residue.